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Red Ox

Red Ox

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Published by Vaibhav Singh

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Published by: Vaibhav Singh on Jul 15, 2010
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10/25/2012

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255REDOX REACTIONS
Chemistry deals with varieties of matter and change of onekind of matter into the other. Transformation of matter fromone kind into another occurs through the various types of reactions. One important category of such reactions is
Redox Reactions
. A number of phenomena, both physicalas well as biological, are concerned with redox reactions. These reactions find extensive use in pharmaceutical, biological, industrial, metallurgical and agricultural areas. The importance of these reactions is apparent from the fact that burning of different types of fuels for obtaining energy for domestic, transport and other commercial purposes,electrochemical processes for extraction of highly reactivemetals and non-metals, manufacturing of chemicalcompounds like caustic soda, operation of dry and wet  batteries and corrosion of metals fall within the purview of redox processes. Of late, environmental issues like
Hydrogen Economy
(use of liquid hydrogen as fuel) anddevelopment of 
‘Ozone Hole’
have started figuring under redox phenomenon.
8.1CLASSICAL IDEA OF REDOX REACTIONS – OXIDATION AND REDUCTION REACTIONS
Originally, the term
oxidation
was used to describe theaddition of oxygen to an element or a compound. Becauseof the presence of dioxygen in the atmosphere (~20%),many elements combine with it and this is the principalreason why they commonly occur on the earth in theform of their oxides. The following reactions represent oxidation processes according to the limited definition of oxidation:2 Mg (s) + O
2
(g)
2 MgO (s)(8.1)S (s) + O
2
(g)
SO
2
(g)(8.2)
 After studying this unit you will beable to
identify redox reactions as a classof reactions in which oxidationand reduction reactions occur simultaneously;
define the terms oxidation,reduction, oxidant (oxidisingagent) and reductant (reducingagent);
explain mechanism of redox reactions by electron transfer process;
use the concept of oxidationnumber to identify oxidant andreductant in a reaction;
classify redox reaction intocombination (synthesis),decomposition, displacement and disproportionationreactions;
suggest a comparative order among various reductants andoxidants;
 balance chemical equationsusing (i) oxidation number (ii) half reaction method;
learn the concept of redox reactions in terms of electrodeprocesses.
UNIT 8
REDOX REACTIONS
 
Where there is oxidation, there is always reduction – Chemistry is essentially a study of redox systems.
 
256CHEMISTR
In reactions (8.1) and (8.2), the elementsmagnesium and sulphur are oxidised onaccount of addition of oxygen to them.Similarly, methane is oxidised owing to theaddition of oxygen to it.CH
4
(g) + 2O
2
(g)
CO
2
(g) + 2H
2
O (l)(8.3) A careful examination of reaction (8.3) in which hydrogen has been replaced by oxygenprompted chemists to reinterpret oxidation interms of removal of hydrogen from it and,therefore, the scope of term oxidation was broadened to include the removal of hydrogenfrom a substance. The following illustration isanother reaction where removal of hydrogencan also be cited as an oxidation reaction.2 H
2
S(g) + O
2
(g)
2 S (s) + 2 H
2
O (l)(8.4) As knowledge of chemists grew, it wasnatural to extend the term oxidation for reactions similar to (8.1 to 8.4), which do not involve oxygen but other electronegativeelements. The oxidation of magnesium withfluorine, chlorine and sulphur etc. occursaccording to the following reactions :Mg (s) + F 
2
(g)
MgF 
2
(s)(8.5)Mg (s) + Cl
2
(g)
MgCl
2
(s)(8.6)Mg (s) + S (s)
MgS (s)(8.7)Incorporating the reactions (8.5 to 8.7) within the fold of oxidation reactionsencouraged chemists to consider not only theremoval of hydrogen as oxidation, but also theremoval of electropositive elements asoxidation. Thus the reaction :2K 
4
[Fe(CN)
6
](aq) + H
2
O
2
(aq)
2K 
3
[Fe(CN)
6
](aq)+ 2 KOH (aq)is interpreted as oxidation due to the removalof electropositive element potassium frompotassium ferrocyanide before it changes topotassium ferricyanide. To summarise, theterm
“oxidation”
is defined as the
additionof oxygen/electronegative element to asubstance or removal of hydrogen/electropositive element from a substance.
In the beginning, reduction wasconsidered as removal of oxygen from a compound. However, the term
reduction
has been broadened these days to include
removalof oxygen/electronegative element from asubstance or addition of hydrogen/electropositive element to a substance.
 According to the definition given above, thefollowing are the examples of reductionprocesses:2 HgO (s) 2 Hg (l) + O
2
(g)(8.8)(removal of oxygen from mercuric oxide )2 FeCl
3
(aq) + H
2
(g)
2 FeCl
2
(aq) + 2 HCl(aq)(8.9)(removal of electronegative element, chlorinefrom ferric chloride)CH
2
= CH
2
(g) + H
2
(g)
H
3
C – CH
3
(g)(8.10)(addition of hydrogen)2HgCl
2
(aq) + SnCl
2
(aq)
Hg
2
Cl
2
(s)+SnCl
4
(aq)(8.11)(addition of mercury to mercuric chloride)In reaction (8.11) simultaneous oxidationof stannous chloride to stannic chloride is alsooccurring because of the addition of electronegative element chlorine to it. It wassoon realised that oxidation and reductionalways occur simultaneously (as will beapparent by re-examining all the equationsgiven above), hence, the word
“redox”
wascoined for this class of chemical reactions.
Problem 8.1
In the reactions given below, identify thespecies undergoing oxidation andreduction:(i) H
2
S (g) + Cl
2
(g)
2 HCl (g) + S (s)(ii) 3Fe
3
O
4
(s) + 8 Al (s)
9 Fe (s)+ 4Al
2
O
3
(s)(iii) 2 Na (s) + H
2
(g)
2 NaH (s)
Solution
(i) H
2
S is oxidised because a moreelectronegative element, chlorine is addedto hydrogen (or a more electropositiveelement, hydrogen has been removedfrom S). Chlorine is reduced due toaddition of hydrogen to it.(ii) Aluminium is oxidised becauseoxygen is added to it. Ferrous ferric oxide
 
257REDOX REACTIONS
(Fe
3
O
4
) is reduced because oxygen has been removed from it.(iii) With the careful application of theconcept of electronegativity only we may infer that sodium is oxidised andhydrogen is reduced.Reaction (iii) chosen here prompts us tothink in terms of another way to defineredox reactions.
8.2REDOX REACTIONS IN TERMS OFELECTRON TRANSFER REACTIONS
 We have already learnt that the reactions2Na(s) + Cl
2
(g)
2NaCl (s)(8.12)2Na(s) + O
2
(g)
Na 
2
O(s)(8.13)2Na(s) + S(s)
Na 
2
S(s)(8.14)are redox reactions because in each of thesereactions sodium is oxidised due to theaddition of either oxygen or moreelectronegative element to sodium.Simultaneously, chlorine, oxygen and sulphur are reduced because to each of these, theelectropositive element sodium has beenadded. From our knowledge of chemical bonding we also know that sodium chloride,sodium oxide and sodium sulphide are ioniccompounds and perhaps better written asNa 
+
Cl
 – 
(s), (Na 
+
)
2
O
2– 
(s), and (Na 
+
)
2
S
2– 
(s).Development of charges on the speciesproduced suggests us to rewrite the reactions(8.12 to 8.14) in the following manner :For convenience, each of the aboveprocesses can be considered as two separatesteps, one involving the loss of electrons andthe other the gain of electrons. As anillustration, we may further elaborate one of these, say, the formation of sodium chloride.2 Na(s)
2 Na 
+
(g)
 
+ 2e
 – 
Cl
2
(g) + 2e
 – 
 
2 Cl
 – 
(g)Each of the above steps is called a half reaction, which explicitly shows involvement of electrons. Sum of the half reactions givesthe overall reaction :2 Na(s) + Cl
2
(g)
2 Na 
+
Cl
 – 
(s) or 2 NaCl (s)Reactions 8.12 to 8.14
suggest that half reactions that involve loss of electrons arecalled oxidation reactions. Similarly, thehalf reactions that involve gain of electronsare called reduction reactions.
It may not  be out of context to mention here that the new  way of defining oxidation and reduction has been achieved only by establishing a correlation between the behaviour of speciesas per the classical idea and their interplay inelectron-transfer change. In reactions (8.12 to8.14) sodium, which is oxidised, acts as
a reducing agent
because it donates electronto each of the elements interacting with it andthus helps in reducing them. Chlorine, oxygenand sulphur are reduced and act as oxidisingagents because these accept electrons fromsodium. To summarise, we may mention that 
Oxidation: 
Loss of electron(s) by any species.
Reduction: 
 
Gain of electron(s) by any species.
Oxidising agent : 
 
 Acceptor of electron(s).
Reducing agent : 
 
Donor of electron(s).
Problem 8.2
 Justify that the reaction :2 Na(s) + H
2
(g)
2 NaH (s) is a redox change.
Solution
Since in the above reaction the compoundformed is an ionic compound, which may also be represented as Na 
+
H
 – 
(s), thissuggests that one half reaction in thisprocess is :2 Na (s)
2 Na 
+
(g) + 2e
 – 

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